Rearrangements and interconversions of heteroatom-substituted isocyanates, isothiocyanates, nitrile oxides, and nitrile sulfides, RX-NCY and RY-CNX

Koch, Rainer, Finnerty, Justin J. and Wentrup, Curt (2011) Rearrangements and interconversions of heteroatom-substituted isocyanates, isothiocyanates, nitrile oxides, and nitrile sulfides, RX-NCY and RY-CNX. Journal of Organic Chemistry, 76 15: 6024-6029. doi:10.1021/jo200593u


Author Koch, Rainer
Finnerty, Justin J.
Wentrup, Curt
Title Rearrangements and interconversions of heteroatom-substituted isocyanates, isothiocyanates, nitrile oxides, and nitrile sulfides, RX-NCY and RY-CNX
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2011-08
Sub-type Article (original research)
DOI 10.1021/jo200593u
Volume 76
Issue 15
Start page 6024
End page 6029
Total pages 6
Place of publication Washington DC, United States
Publisher American Chemical Society
Collection year 2012
Language eng
Formatted abstract
Isocyanates and isothiocyanates of the type RX—NCY (X and Y = O or S) and the isomeric nitrile oxides and nitrile sulfides RY—CNX are highly reactive compounds. A number of potential 1,4-shifts of substituent groups of the type R—Y—CNX→R—X—N=C=Y, 1,3-shiftsR—C(=Y)—N=X→R—X—N=C=Y, and 1,2-shifts R—C(=Y)N=X → R—Y—CNX have been evaluated computationally. The results obtained for the relatively new functional MPW1K and the wellestablished B3LYP, together with a triple-ζ quality basis set, are very similar. The 1,3- and 1,4-halogen shifts in the title compounds are usually highly exothermic and possess low activation barriers. 1,3-Aryl shifts are feasible for for 5e6e (Ar—CO—NSO2 → Ar—SO2—NCO) with activation barriers of less than 40 kcal/mol. Additionally, several 1,3- and 1,4-hydrogen shifts and the 1,4-methyl-shift in methoxynitrile sulfide MeO—CNS to methylsulfenyl isocyanate MeS—NCO (4c6c) are potentially feasible. The 1,2-shift reactions 4b5b (HO—NCS→H—CSNO) and 4c → 5c (Ar—O—CNS → Ar—CO—NS) are good candidates for experimental observation with activation energies around 30 kcal/mol. 
Keyword Molecular-Orbital Methods
Uber Thioacyl-Isocyanate
Flash Vacuum Pyrolysis
Ketene-Ketenimine Rearrangements
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
School of Chemistry and Molecular Biosciences
 
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